Insecticide-fungicide and process for making the same



Patented'yMar. 30, 1926; l

NI-Tao STATES-A PATENT OFFICE,

EDWARD C. BOLTON, OF OLMSTED FALLS, OHIO, 'ASSIGNOR TO THE SHERWIN-WIL- LIAMS COMPANY, CLEVELAND, OHIO, A CORPORATION OF OHIO.

, IN SECTICIDE-FUNGICIDE AN D PROCESS FOR) MAKING THE SAME.

1T0 Drawing.

To all whom it may concern:

Be it known that I, EDWARD 0. Homes, a citizen of the United States, and a resident 5 State of Ohio, have invented certain new and useful Improvements in Insecticide- F ungicide and, Processesfor. Making the Same, of which the following is a specification, I

This invention relates toproducts intended for use as a fungicide-insecticide, and to the process for making same.

From the earliest days of horticulture sulfur has been used as an insectifuge, in-

" secticide and fungicide and, during recent years, its'use has been greatly extended. It is well known that a finely divided sulfur is more eflicient for these purposes than the coarser forms and, therefore, various methods have heretofore been devised to' produce the finely divided-sulfur. This has "been accomplished by dry-grinding in impact mills and ball mills, as well as mills of other types; also by wet-grinding in the same, as

' Well as by sublimation.

Very finely divided sulfur prepared by chemical methods such as by the reaction between sulfur dioxide and hydrogen sulfide, which" reaction may be.

represented as follows:

..SO,+2H,S,=2H O+3S The above reaction may occur either inv the gaseous phase or, better still, aqueous solutions.

Another common method of preparing finely, divided sulfur is to decompose a olysulfid in aqueous solution, with an acid has also been,

although "ration, crystallization, etc.

Application filed March 8; 1924 Serial No. 697,713.

are soluble in water so that theymay be washed away. These reactions mayv be represented thus of Olmsted Falls, county of Cuyahoga,

If, instead of using a polysulfidofan alkali, a polysulfid of an element of the alkaline earths group, such as calcium polysiilfid or barium polysulfid, is usedfa number of different acids may be used as 'precipitants but sulfuric acid should. not be used if it is desired to produce a pure sulfur, becausethe'sulfates of the, elements of the alkaline earths group are insoluble or but slightly soluble in water, "and hence will be coprecipitated-with the sulfur and cannot be economically separated therefrom.

Ithas been found that the sulfates of the elements of the alkaline earths group are practically worthless as insecticidesv and fungicides, but a sulfur coprecipitated with these is, nevertheless, of somewhat greater value for these purposes, than if it were mixed wlth an-equal volume of other inert mineral matter. The reactions which form these sulfates may be represented thus:

CaS +H,SO,T: CaSO,|-H S+ (x-l) S BaS +H SO,:- BaSQ,l-H S+ (x1) S If hydrochloric acid is used with "a polysulfid of an ,element of the alkaline earths group, thereactions with calcium, strontium and barium representedthus z, v

OaS,+2HCl=CaC1,+H,-|- a1 S SrSx+2HCl=SrCl -}H S+ (ir-1) S BaS,+2HCl=BaCl,+- H,S+ (x -1 S Since the calcium chloride, strontium chloride and barium chloride produced by the above reactions, are-soluble in water, the sulfur may be removed in a state of purity as in the case of the polysulfids of the alkalies.

If desired, the chlorides of the elements of the alkaline earths group, may be recovered from the solution byprocesses of evapo- The substantial- 1y pure sulfur obtained is in a finely divided polysulfids may be state and when kept in a wet condition is a very reactive substance and a very eflicient insecticide-fungicide. However, ,When this sulfur is once dried it is rathertroublesome to completely disintegrate the aggregated particles and thus make it. suitable for dust mg, alone, or in dry mixtures, and at the same time have it possess the property of being readily wet-table with water.

When used in wetsprays it is very desirable' that the sulfur should be readily wettable with water and this may be accomplished by some'such method as is disclosed in my patent application, Serial N 0. 565,434,

wherein there is disclosed the use of bentonite for this purpose. 7

If the active form of sulfur, above re-' ferred to,is prepared by the reaction of sulfuric acid on a polysulfid of an element of thealkaline earths group, there is coprecipitated' with the sulfur, as has already been stated, a sulfate of an element of the alkaline earths group rand, although there sulfates are practically worthless as insecticides andfungicides and must be classed as inerts under the existing Federal insecticide law, yet'they do possess some merit. in

the mixture since they tend to keep the sulfur particles somewhatdispersed and in a more reactive condition, and the copreclpitate, after bein dried, is more easily wettable than sul ur' alone. Insecticidesand fungicides, generally, are more easily handled in commerce in the dry powdered form and it is an object of this invention to produce aproduct that'may I be thus handled and still be readily 'wettable with water.

It is a further object of my invention to providea mixture of fungicidal and insecticidal sulfur and an insoluble or but slightly soluble toxic compound of an element of the alkaline earths group in which the sulfur is maintained in' its highly reactive state and is readily wettable with water. It is a further object of the invention toprovide a process for manufacturing this product on a commercial scale by forming the mixture 4 as .a coprecipitate resulting frdm the reacsulfid of an element of the alkaline ion of a suitable acid substance on a polygroup.

My invention is not limited to the use ofthe polys'ulfid of any particular element of the alkaline earths group, nor to any single acid substance, but relates, broadly, tothe 'coprecipitation, with the sulfur, of insoluble I or but slightly soluble compounds possessin "fungicidal and insecticidal properties, whic may be classed as more than 95% active under the existing "Federal insecticide law.

''As illustrations of a few of the possible ap-- -plications of my invention, the following are given: 1

Using the letter E to represent an element earths group and the letter x to represent a number greater than one,

of the alkaline earths l but not greater than five, the reactions may be written thus In the typical reactions just' given, it will be noted that, there is a development of hydrogen sulfid. It is desirable that the sulfur in this hydrogen sulfid be utilized, and,

preferably in insecticidal compositions. To accomplish this it ma be brought directly into contact with sul ur dioxide or sulfites and thiosulfates; of the elements of the alkalowing reactions. These reactions may take place in steps, separately or all together, almost simultaneously,'the final result being that practically all of the sulfur is recovered in the desired 'form. Thesereacti'ons may be considered astypes to illustrate this:

The combined reactions may be written '2ES,;]- SO +2H SsO 2ESeO,+2H O(2x+1)S erated but the sulfur therein ered as already described.

In practising m invention the chemicals are brought toget er. in solution in proper proportion to carry out the'reactions stated line earths group, as illustrated in the fol ioo may be recov-.

and thecoprecipitate of sulfur and the com- 4 pound of the element ofthe alkaline earths group is separated ffom the water by theunderstood that this is intended torefer to the condition of insolubility or but slight solubility referred to hereinabove.

Having thus described my invention, what Iclaim is:

1, In methods for the production of .a product for the purposes specified, the step which consists in reacting upon a polysulfid of an element of the alkaline earths group with a suitable acid substance for producing a coprecipitate 'of finely divided sulfur and a substantially insoluble toxic substance.

2. In methods forthe production of a product for the purposes specified, the step which consists in reacting upon a polysulfid of an element of the alkaline earths group with a suitable acid substance for producing hydrogen sulfid and a coprecipitate of finely divided sulfur and a substantially insoluble toxic substance, and reacting upon the hydrogen sulfid with another sulfur compound to form anadditional amount of finely divided sulfur.

S. In methods for the production of a product for the purposes specified, the step drogeri sulfid with sulfur dioxide to form an additional amount of finely divided sulfur.

4. In methods for the production of a product for the purposes specified, the step which consists in "forming a coprecipitate of finely divided sulfur and a substantially insoluble toxic substance by bringing together in solution a polysulfid of an element of the alkaline earths group, sulfur dioxide and an acid substance. capable of reacting on said polysulfid to form said toxic substance.

5. In methods for the production of aproduct for the" purposes specified, the step in which an acid capable of forming a sub' stantially, insoluble toxic compound of an element of the alkaline earths group reacts with a sulfite or thiosulfate of an element of the alkaline earths group in admixture with a polysulfid of an element'of the alkaline earths group to form a coprecipitate of sulfur and :said toxic compound.

6. As a new product or article of manufacture, a co-precipitate of finely divided sulfur and a substantially insoluble compound of an element of the alkaline earths group.

which consists in reacting upon a polysulfidof an element of the alkaline earths group with a suitable acidsubstance for producing hydrogen sulfid and a coprecipitate of finely divided sulfur and a substantiallyinsoluble.

toxic substance, and reacting upon the hy- 7. As a new product 01' article of manufacture, for the purposes specified, a dry powder consisting of a co-precipitate of sulfu" and a substantially insoluble insectialkaline earths group.

8. As anew product or article of manufacture, for the purposes. specified, a dry powder of which the minor part consists of chemicallyprecipitated sulfur arid the major part consists of a substantially insoluble compound of an element -,of the alkaline fifths group co-precipitated with the sul- In testimony whereof I aflix my signature.

EDWARD C. -HOLTON.-

cidal t io compound of an element of the 

